Cationically modified comb polymers based on acryloyldimethyl taurine acid

ABSTRACT

The invention provides water-soluble or water-swellable copolymers obtained by free-radical copolymerization of
     A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,   B) optionally, one or more other olefinically unsaturated, noncationic, optionally crosslinking comonomers containing at least one oxygen, nitrogen, sulfur or phosphorus atom and possessing a molecular weight of less than 500 g/mol,   C) one or more mono- or polyolefinically unsaturated, optionally crosslinking macromonomers each possessing at least one oxygen, nitrogen, sulfur or phosphorus atom and having a number-average molecular weight of greater than or equal to 200 g/mol, and   D) one or more olefinically unsaturated, cationic comonomers containing at least one oxygen, nitrogen, sulfur or phosphorus atom and possessing a molecular weight of less than 500 g/mol, the copolymerization   E) taking place in the presence or absence of at least one polymeric additive having number-average molecular weights of from 200 g/mol to 10 9  g/mol.   

     The water-soluble or water-swellable copolymers of the present invention are useful in formulating cosmetics.

The present invention relates to cationically modified comb polymersbased on acryloyldimethyltaurine and/or acryloyldimethyltaurates.

Consumer desires and cosmetic product rheology are closely interlinked.For example, the appearance of a cream or lotion is influenced by theviscosity. The sensorial properties, such as consistency orspreadability, determine the individual profile of a cosmetic product.The effectiveness of active substances (e.g., sun protection filters)and also the storage stability of the formulation are closely dependenton the rheological properties of the product.

In cosmetics, polyelectrolytes play a key part as thickeners and gelformers. State of the art are in particular the polyacrylic acids,prepared on the basis of poly(meth)acrylic acid, and the water-solublecopolymers thereof. The diversity of possible structures and theassociated diverse possibilities for use are reflected in a host ofpatent applications.

A substantial disadvantage of thickeners based on poly(meth)acrylic acidis the heavy pH dependence of the thickening effect. Thus, generallyspeaking, adequate viscosity is only achieved when the pH of theformulation is above 6, i.e., the poly(meth)acrylic acid is inneutralized form. Further, the corresponding gels/formulation aresensitive to UV radiation and shearing and additionally impart a stickysensation on the skin. Since the thickeners are generally in acidicform, moreover, an additional neutralization step is needed in thecourse of formulation.

In the 1990s, innovative thickeners based on acryloyldimethyltaurineand/or its salts were introduced into the market (EP-B-0 815 828, EP-B-0815 844, EP-B-0 815 845, EP-B-0 829 258, EP-A-0 850 642 and EP-A-0 919217). Both in the form of the preneutralized homopolymer and also ascorresponding copolymers (®ARISTOFLEX AVC CLARIANT GmbH) such thickenersare in many respects superior to the poly(meth)acrylate thickeners. Forinstance, they exhibit an outstanding profile of properties even in pHranges below pH 6, i.e., a range within which it is no longer possibleto operate with conventional poly(meth)acrylate thickeners. High UVstability and shearing stability, outstanding viscoelastic properties,great ease of processing, and a favorable toxicological profile of theprincipal monomer imbue these thickeners with a high applicationpotential.

The applicant has surprisingly succeeded in obtaining novel cationicallymodified comb polymers based on acryloyldimethyltaurine (AMPS) whichexhibit very good thickening and emulsifying/dispersing properties incombination with high pH stability. In both crosslinked andnoncrosslinked form the comb polymers of the invention open up a broadapplication spectrum. The polymers of the invention put the user for thefirst time in a position to combine the synergistic properties ofhydrophobically modified anionic polymers with the advantages (as isknown) of cationic charges.

The invention provides water-soluble or water-swellable copolymersobtainable by free-radical copolymerization of

-   A) acryloyldimethyltaurine and/or acryloyldimethyltaurates,-   B) if desired, one or more other olefinically unsaturated,    noncationic, optionally crosslinking comonomers containing at least    one oxygen, nitrogen, sulfur or phosphorus atom and possessing a    molecular weight of less than 500 g/mol,-   C) one or more mono- or polyolefinically unsaturated, optionally    crosslinking macromonomers each possessing at least one oxygen,    nitrogen, sulfur or phosphorus atom and having a number-average    molecular weight of greater than or equal to 200 g/mol, and-   D) one or more olefinically unsaturated, cationic comonomers    containing at least one oxygen, nitrogen, sulfur or phosphorus atom    and possessing a molecular weight of less than 500 g/mol, the    copolymerization-   E) taking place in the presence or absence of at least one polymeric    additive having number-average molecular weights of from 200 g/mol    to 10⁹ g/mol.

The copolymers of the invention preferably possess a molecular weight offrom 10³ g/mol to 10⁹ g/mol, more preferably from 10⁴ to 10⁷ g/mol, verypreferably from 5*10⁴ to 5*10⁶ g/mol.

The acryloyldimethyltaurates can be the organic or inorganic salts ofacryloyldimethyltaurine. Preference is given to the Li⁺, Na⁺, K⁺, Mg⁺⁺,Ca⁺⁺, Al⁺⁺⁺ and/or NH₄ ⁺ salts. Likewise preferred are themonoalkylammonium, dialkylammonium, trialkylammonium and/ortetraalkylammonium salts, in which the alkyl substituents of the aminesmay independently of one another be (C₁–C₂₂)-alkyl radicals or(C₂–C₁₀)-hydroxyalkyl radicals. Preference is also given to mono- totriethoxylated ammonium compounds with a different degree ofethoxylation. It should be noted that the invention also embracesmixtures of two or more of the abovementioned representatives.

The degree of neutralization of the acryloyldimethyltaurine can bebetween 0 and 100%, particular preference being given to a degree ofneutralization of more than 80%.

Based on the total mass of the copolymers, the amount ofacryloyldimethyltaurine and/or acryloyldimethyltaurates is at least 0.1%by weight, preferably from 20 to 99.5% by weight, more preferably from50 to 98% by weight.

As comonomers B) it is possible to use all olefinically unsaturatednoncationic monomers whose reaction parameters allow copolymerizationwith acryloyldimethyltaurine and/or acryloyldimethyltaurates in therespective reaction media.

Preferred comonomers B) are unsaturated carboxylic acids and theiranhydrides and salts, and also their esters with aliphatic, olefinic,cycloaliphatic, arylaliphatic or aromatic alcohols having a carbonnumber of from 1 to 22.

Particularly preferred unsaturated carboxylic acids are acrylic acid,methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid,crotonic acid, itaconic acid, and senecic acid.

Preferred counterions are Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺, NH₄ ⁺,monoalkylammonium, dialkylammonium, trialkylammonium and/ortetraalkylammonium radicals, in which the alkyl substituents of theamines independently of one another can be (C₁–C₂₂)-alkyl radicals or(C₂–C₁₀)-hydroxyalkyl radicals. It is additionally possible to employmono- to triethoxylated ammonium compounds with a different degree ofethoxylation. The degree of neutralization of the carboxylic acids canbe between 0 and 100%.

Further preferred comonomers are open-chain N-vinyl amides, preferablyN-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide(VIMA) and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams)with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) andN-vinylcaprolactam; amides of acrylic and methacrylic acid, preferablyacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, and N,N-diisopropylacrylamide; alkoxylatedacrylamides and methacrylamides, preferably hydroxyethyl methacrylate,hydroxymethylmethacrylamide, hydroxyethylmethacrylamide,hydroxypropylmethacrylamide, and mono[2-(methacryloyloxy)ethyl]succinate; N,N-dimethylamino methacrylate;diethylaminomethyl methacrylate; acrylamido- and methacrylamidoglycolicacid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate;styrene; acrylonitrile; vinyl chloride; stearyl acrylate; laurylmethacrylate; vinylidene chloride; and/or tetrafluoroethylene.

Likewise suitable comonomers B) are inorganic acids and their salts andesters. Preferred acids are vinylphosphonic acid, vinylsulfonic acid,allylphosphonic acid, and methallylsulfonic acid.

The weight fraction of the comonomers B), based on the total mass of thecopolymers, can be from 0 to 99.7% by weight and is preferably from 0.5to 80% by weight, more preferably from 2 to 50% by weight.

In accordance with the invention at least one so-called macromonomer C)is employed in the copolymerization. The macromonomers are at leastsingly olefinically functionalized polymers having one or more discreterepeating units and a number-average molecular weight of greater than orequal to 200 g/mol. In the copolymerization it is also possible to usemixtures of chemically different macromonomers C). The macromonomers arepolymeric structures composed of one or more repeating units and have amolecular weight distribution characteristic of polymers.

Preferred macromonomers C) are compounds of formula (I).R¹—Y-[(A)_(v)-(B)_(w)-(C)_(x)-(D)_(z)]-R²  (I)

R¹ represents a polymerizable function from the group of the vinylicallyunsaturated compounds which are suitable for constructing polymericstructures by a free-radical route. Preferably R¹ is a vinyl, allyl,methallyl, methylvinyl, acryloyl (CH₂═CH—CO—), methacryloyl(CH₂═C[CH₃]—CO—), crotonyl, senecionyl, itaconyl, maleyl, fumaryl orstyryl radical. Attachment of the polymer chain to the reactive endgroup requires a suitable bridging group Y. Preferred bridges Y are —O—,—C(O)—, —C(O)—O—, —S—, —O—CH₂—CH(O—)—CH₂OH, —O—CH₂—CH(OH)—CH₂O—,—O—SO₂—O—, —O—SO₂—O—, —O—SO—O—, —PH—, —P(CH₃)—, —PO₃—, —NH—, and—N(CH₃)—, more preferably —O—.

The polymeric central moiety of the macromonomer is represented by thediscrete repeating units A, B, C, and D. Preferred repeating units A, B,C, and D are derived from acrylamide, methacrylamide, ethylene oxide,propylene oxide, AMPS, acrylic acid, methacrylic acid, methylmethacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene,1,3-butadiene, isoprene, isobutene, diethylacrylamide, anddiisopropylacrylamide.

The indices v, w, x, and z in formula (I) represent the stoichiometriccoefficients relating to the repeating units A, B, C, and D. v, w, x,and z amount independently of one another to from 0 to 500, preferably 1to 30, it being necessary for the sum of the four coefficients onaverage to be ≧1.

The distribution of the repeating units over the macromonomer chain canbe random, blocklike, alternating or gradientlike.

R² denotes a linear or branched aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁–C₅₀) hydrocarbon radical, OH, —NH₂,—N(CH₃)₂ or is the structural unit [—Y—R¹].

In the case of R² being [—Y—R¹] the macromonomers in question aredifunctional and suitable for crosslinking the copolymers.

Particularly preferred macromonomers C) are acrylically ormethacrylically monofunctionalized alkyl ethoxylates of formula (II).

R³, R⁴, R⁵, and R⁶ are independently of one another hydrogen orn-aliphatic, isoaliphatic, olefinic, cycloaliphatic, arylaliphatic oraromatic (C₁–C₃₀) hydrocarbon radicals.

Preferably R³ and R⁴ are H or —CH₃, more preferably H; R⁵is H or —CH³;and R⁶ is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic,arylaliphatic or aromatic (C₁–C₃₀) hydrocarbon radical.

v and w are in turn the stoichiometric coefficients relating to theethylene oxide units (EO) and propylene oxide units (PO). v and w amountindependently of one another to from 0 to 500, preferably 1 to 30, itbeing necessary for the sum of v and w to be on average ≧1. Thedistribution of the EO and PO units over the macromonomer chain can berandom, blocklike, alternating or gradientlike. Y stands for theabovementioned bridges.

Particularly preferred macromonomers C) have the following structure inaccordance with formula (II):

Name R³ R⁴ R⁵ R⁶ V W ® LA-030 H H —CH₃ -lauryl 3 0 methacrylate ® LA-070H H —CH₃ -lauryl 7 0 methacrylate ® LA-200 H H —CH₃ -lauryl 20 0methacrylate ® LA-250 H H —CH₃ -lauryl 25 0 methacrylate ® T-080methacrylate H H —CH₃ -talc 8 0 ® T-080 acrylate H H H -talc 8 0 ® T-250methacrylate H H —CH₃ -talc 25 0 ® T-250 crotonate —CH₃ H —CH₃ -talc 250 ® OC-030 H H —CH₃ -octyl 3 0 methacrylate ® OC-105 H H —CH₃ -octyl 105 methacrylate ® Behenyl-010- H H H -behenyl 10 0 methylaryl® Behenyl-020- H H H -behenyl 20 0 methylaryl ® Behenyl-010- —CH₃ —CH₃ H-behenyl 10 0 senecionyl ® PEG-440 diacrylate H H H -acryloyl 10 0® B-11-50 H H —CH₃ -butyl 17 13 methacrylate ® MPEG-750 H H —CH₃ -methyl18 0 methacrylate ® P-010 acrylate H H H -phenyl 10 0 ® O-050 acrylate HH H -oleyl 5 0

The molecular weight of the macromonomers C) is preferably from 200g/mol to 10⁶ g/mol, more preferably from 150 to 10⁴ g/mol, and verypreferably from 200 to 5 000 g/mol.

The weight fraction of the macromonomer F), based on the total mass ofthe copolymers, is from 0.1 to 99.8% by weight, more preferably from 2to 90% by weight, and very preferably from 5 to 80% by weight.

Essential to the invention is that the copolymers include in theirstructure at least one cationic comonomer D). Suitable comonomers D)include all olefinically unsaturated monomers with cationic charge whichare capable of forming copolymers with acryloyldimethyltaurine or itssalts in the chosen reaction media. The resulting distribution of thecationic charges across the chains can be random, alternating, blocklikeor gradientlike. It may be noted that the cationic comonomers D) alsocomprehend those which bear the cationic charge in the form of a betainestructure. Comonomers D) for the purposes of the invention are alsoamino-functionalized precursors which can be converted into theircorresponding quaternary derivatives by polymer-analogous reactions(e.g., reaction with DMS).

Particularly preferred comonomers D) are

diallyldimethylammonium chloride (DADMAC),

[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC),

[2-(acryloyloxy)ethyl]trimethylammonium chloride,

[2-methacrylamidoethyl]trimethylammonium chloride,

[2-(acrylamido)ethyl]trimethylammonium chloride,

N-methyl-2-vinylpyridinium chloride and/or

N-methyl4-vinylpyridinium chloride.

The weight fraction of the comonomers D), based on the total mass of thecopolymers, is preferably from 0.1 to 99.8% by weight, more preferablyfrom 0.5 to 30% by weight, and very preferably from 1 to 20% by weight.

In one other preferred embodiment the copolymerization is conducted inthe presence of at least one polymeric additive E), the additive E)being added wholly or partly in solution to the polymerization mediumbefore the actual copolymerization. The use of two or more additives E)is likewise in accordance with the invention. Crosslinked additives E)may likewise be used.

The additives E) or mixtures thereof must only be wholly or partlysoluble in the chosen polymerization medium.

During the actual polymerization step the additive E) has a number offunctions. On the one hand it prevents the formation of overcrosslinkedpolymer fractions in the copolymer which forms in the actualpolymerization step, and on the other hand the additive E) isstatistically attacked by active free radicals in accordance with thevery well-known mechanism of graft copolymerization. Depending on theparticular additive E), this results in greater or lesser fractions ofthe additive being incorporated into the copolymers. Moreover, suitableadditives E) possess the property of altering the solution parameters ofthe copolymers which form during the free-radical polymerizationreaction in such a way that the average molecular weights are shifted tohigher values. As compared with analogous copolymers prepared withoutthe addition of the additives E), those prepared with the addition ofadditives E) advantageously exhibit a significantly higher viscosity inaqueous solution.

Preferred additives E) are homopolymers and copolymers which are solublein water and/or alcohols. The term “copolymers” also comprehends thosehaving more than two different monomer types.

Particularly preferred additives E) are homopolymers and copolymers ofN-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, ethylene oxide,propylene oxide, acryloyldimethyltaurine, N-vinylcaprolactam,N-vinylmethylacetamide, acrylamide, acrylic acid, methacrylic acid,N-vinylmorpholide, hydroxyethyl methacrylate, diallyldimethylammoniumchloride (DADMAC) and/or [2-(methacryloyloxy)ethyl]trimethylammoniumchloride (MAPTAC); polyalkylene glycols and/or alkylpolyglycols.

Particularly preferred additives E) are polyvinylpyrrolidones (e.g.,K15®, K20® and K30® from BASF), poly(N-vinylformamides),poly(N-vinylcaprolactams), and copolymers of N-vinylpyrrolidone,N-vinylformamide and/or acrylic acid, which may also have been partly orfully hydrolyzed.

The molecular weight of the additives E) is preferably from 10² to 10⁷g/mol, more preferably from 0.5*10⁴ to 10⁶ g/mol.

The amount in which the polymeric additive E) is used, based on thetotal mass of the monomers to be polymerized during thecopolymerization, is preferably from 0.1 to 90% by weight, morepreferably from 1 to 20% by weight, and with particular preference from1.5 to 10% by weight.

In one further preferred embodiment the copolymers of the invention arecrosslinked, i.e., they contain comonomers containing at least twopolymerizable vinyl groups.

Preferred crosslinkers are methylenebisacrylamide;methylenebismethacrylamide; esters of unsaturated monocarboxylic andpolycarboxylic acids with polyols, preferably di-acrylates andtriacrylates and -methacrylates, more preferably butanediol and ethyleneglycol diacrylate and -methacrylate, trimethylolpropane triacrylate(TMPTA) and trimethylolpropane trimethacrylate (TMPTMA); allylcompounds, preferably allyl (meth)acrylate, triallyl cyanurate, diallylmaleate, polyallyl esters, tetraallyloxyethane, triallylamine,tetraallylethylenediamine; allyl esters of phosphoric acid; and/orvinylphosphonic acid derivatives.

A particularly preferred crosslinker is trimethylolpropane triacrylate(TMPTA).

The weight fraction of crosslinking comonomers, based on the total massof the copolymers, is preferably up to 20% by weight, more preferablyfrom 0.05 to 10% by weight, and very preferably from 0.1 to 7% byweight.

The polymerization medium used may comprise all organic or inorganicsolvents which have a very substantially inert behavior with respect tofree-radical polymerization reactions and which advantageously allow theformation of medium or high molecular weights. Those used preferablyinclude water; lower alcohols; preferably methanol, ethanol, propanols,iso-, sec- and t-butanol, very preferably t-butanol; hydrocarbons having1 to 30 carbon atoms, and mixtures of the aforementioned compounds.

The polymerization reaction takes place preferably in the temperaturerange between 0 and 150° C., more preferably between 10 and 100° C.,either at atmospheric pressure or under elevated or reduced pressure. Ifdesired the polymerization may also be performed under an inert gasatmosphere, preferably under nitrogen.

In order to initiate the polymerization it is possible to usehigh-energy electro-magnetic rays, mechanical energy, or the customarychemical polymerization initiators, such as organic peroxides, e.g.,benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketoneperoxide, cumene hydroperoxide, dilauroyl peroxide or azo initiators,such as azodiisobutyronitrile (AIBN), for example. Likewise suitable areinorganic peroxy compounds, such as (NH₄)₂S₂O₈, K₂S₂O₈ or H₂O₂, forexample, where appropriate in combination with reducing agents (e.g.,sodium hydrogensulfite, ascorbic acid, iron(II) sulfate, etc.) or redoxsystems comprising as reducing component an aliphatic or aromaticsulfonic acid (e.g., benzenesulfonic acid, toluenesulfonic acid, etc.).

The polymerization reaction can be conducted, for example, as aprecipitation polymerization, emulsion polymerization, bulkpolymerization, solution polymerization or gel polymerization.Particularly advantageous for the profile of properties of thecopolymers of the invention is precipitation polymerization, preferablyin tert-butanol.

The polyfunctional polymers of the invention possess a great structuraldiversity and, consequently, broad potential possibilities for use,which can be tailored to virtually any task where interface effectsand/or surface effects play a part. The term “custom-tailored polymers”gives a vivid description of the possibilities which this new class ofpolymer affords the user.

The presence of cationic charges in the polymer framework makes itpossible to make purposive exploitation of adhesion effects in relationto anionic surfaces. The combination of basic properties which are insome cases completely contradictory, such as, for example, watersolubility and oil solubility or anionic and cationic charges in onesingle molecule, opens up the path to water-soluble association polymershaving completely new kinds of profiles of properties. An example thatwill be given at this point is the strikingly high electrolyte stabilityof thickener systems based on the copolymers of the invention, allowingthem to be used as “superabsorbents” for electrolyte-containingsolutions. This is in contrast to the low salt stability of manywater-absorbing hygiene articles based on crosslinked, fully or partlyneutralized polyacrylic acids.

The following examples are intended to illustrate the invention without,however, restricting it thereto.

EXAMPLE 1

Reactants amount (g) NH₃-neutralized AMPS 80 ® Genapol-BE-010methacrylate 15 DADMAC 5 t-Butanol 400 Dilauroyl peroxide (initiator) 1

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating to60° C., the reaction was initiated by addition of DLP. The polymer wasisolated by removal of the solvent under suction and by subsequentvacuum drying.

The polymer in 1% strength solution in distilled water gave a viscosityof 11 000 mPas.

EXAMPLE 2

Reactants amount (g) NH₃-neutralized AMPS 70 N-Vinylpyrrolidone 5® Genapol-T-250 methacrylate 15[2-(Methacryloyloxy)ethyl]trimethylammonium chloride 10 Water 500Na₂S₂O₈ (initiator) 1 Poly-N-vinylpyrrolidone (® K-15, BASF) 4

The polymer was prepared by the gel polymerization method in water. Themonomers were dissolved in water, the reaction mixture was renderedinert, and then, after initial heating to 70° C., the reaction wasinitiated by addition of sodium peroxodisulfate. The polymer gel wassubsequently comminuted and the polymer was isolated by vacuum drying.

EXAMPLE 3

Reactants amount (g) AMPS 80 ® Genapol-T-250 methacrylate 20[2-(Methacrylamido)ethyl]trimethylammonium chloride 25 Cyclohexane 200Water 300 ® Span 80 1 Na₂S₂O₈ (initiator) 1

The polymer was prepared by the emulsion method in water. The monomerswere emulsified in water/cyclohexane using Span 80®, the reactionmixture was rendered inert using N₂, and then, after initial heating to60° C., the reaction was initiated by addition of sodiumperoxodisulfate. The polymer emulsion was subsequently evaporated down(cyclohexane acting as azeotrope former for water) and the polymer wasisolated.

EXAMPLE 4

Reactants amount (g) NH₃-neutralized AMPS 80 MPEG-750 methacrylate 15N-Methyl-4-vinylpyridinium chloride 5 t-Butanol 300 TMPTA 1.8 AIBN(initiator) 1

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating to68° C., the reaction was initiated by addition of AIBN. The polymer wasisolated by removal of the solvent under suction and by subsequentvacuum drying.

EXAMPLE 5

Reactants amount (g) Na-neutralized AMPS 80 MPEG-750 methacrylate 15® Genapol-O-150 methacrylate 15[2-(Methacryloyloxy)ethyl]trimethylammonium chloride 5 DADMAC 5 Water300 H₂O₂/iron (initiator) 1 Poly[N-vinylcaprolactam] 5

The polymer was prepared by the solution method in water. The monomerswere dissolved in water, the reaction mixture was rendered inert, andthen, after initial heating to 55° C., the reaction was initiated bymeans of an iron(II) sulfate/H₂O₂ redox couple. The polymer solution wassubsequently evaporated down and the polymer was then isolated by vacuumdrying.

EXAMPLE 6

Reactants amount (g) NH₃-neutralized AMPS 80 ® Genapol-LA-040methacrylate 20 [2-(Acrylamido)ethyl]trimethylammonium 25 chloridet-Butanol 500 TMPTA 1.8 Dilauroyl peroxide 2 Poly[N-vinylformamide] 1

The polymer was prepared by the precipitation method in tert-butanol.The monomers in t-butanol were introduced as an initial charge, thereaction mixture was rendered inert, and then, after initial heating,the reaction was initiated by addition of DLP. The polymer was isolatedby removal of the solvent under suction and by subsequent vacuum drying.

Chemical Designation of the Products Employed

TMPTA Trimethylolpropane triacrylate AIBN Azoisobutyronitrile DLPDilauroyl peroxide ® Genapol-T-250 methacrylate Methacrylic acid C₁₆/C₁₈alcohol ethoxylate ester ® Genapol-LA-070 methacrylate Methacrylic acidC₁₂/C₁₄ alcohol ethoxylate ester (7EO) NH₃-neutralized AMPS2-Acrylamido-2-methyl-1-amidopropanesulfonic acid (ammonium salt) ® Span80 Sorbitan ester MPEG-750 methacrylate Methacrylic acid methylethoxylate ester (750 g/mol) ® Genapol-O-150 methacrylate Methacrylicacid oleyl ethoxylate ester ® Genapol-LA-250 methacrylate Methacrylicacid C₁₂/C₁₄ alcohol ethoxylate ester (25EO) ® Genapol-LA-030methacrylate Methacrylic acid C₁₂/C₁₄ alcohol ethoxylate ester (3EO)® Genapol-LA-040 methacrylate Methacrylic acid C₁₂/C₁₄ alcoholethoxylate ester (4EO)

1. A water-soluble or water-swellable copolymer obtained by free-radicalcopolymerization of A) 50 to 99.5% by weight of acryloyldimethyltaurineand/or acryloyldimethyltaurate based on a total weight of saidcopolymer, said acryloyldimethyltaurine and/or acryloyldimethyltauratehaving a degree of neutralization of more than 80%, B) optionaly, one ormore other olefinically unsaturated, noncationic, comonomer containingat least one oxygen, nitrogen, sulfur or phosphorus atom and having amolecular weight of less than 500 g/mol, C) one or more mono- orpolyolefinically unsaturated, macromonomer each having at least oneoxygen, nitrogen, sulfur or phosphorus atom and having a number-averagemolecular weight of greater than or equal to 200 g/mol, and D) one ormore olefinically unsaturated, cationic comonomer containing at leastone oxygen, nitrogen, sulfur or phosphorus atom and having a molecularweight of less than 500 g/mol, the copolymerization E) taking place inthe absence of at least one polymeric additive having number-averagemolecular weights of from 200 g/mol to 10⁹ g/mol.
 2. The water-solubleor water-swellable copolymer as claimed in claim 1, wherein themacromonomer C) is of the formula (I)R¹—Y-[(A)_(v)—(B)_(w)-(C)_(x)-(D)_(z)]-R²   (I) where R¹ a polymerizablefunction from a vinylically unsaturated compound; Y is a bridging group;A, B, C, and D independently of one another are discrete chemicalrepeating units; v, w, x, and z independently of one another amount tofrom 0 to 500, the sum of v, w, x, and z being on average ≧1; and R² isa linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphaticor aromatic (C₁–C₅₀) hydrocarbon radical, OH, —NH₂ or —N(CH₃)₂ or is[—Y—R¹].
 3. The water-soluble or water-swellable copolymer as claimed inclaim 2, wherein the macromonomer C) a compound of formula (II)

in which R³, R⁴, R⁵, and R⁶ are independently of one another hydrogen,n-aliphatic, iso-aliphatic, cycloaliphatic, olefinic, arylaliphaticand/or aromatic radicals having a carbon number of from 1 to 30, EO isan ethylene oxide unit, and PO is a propylene oxide unit, and v and windependently of one another are from 0 to 500, the sum of v and w beingon average ≧1.
 4. The water-soluble or water-swellable copolymer ofclaim 1, wherein the comonomer D) is selected from the group consistingof diallyldimethylammonium chloride,[2-(methacryloyloxy)ethyl]trimethylammonium chloride,[2-(acryloyloxy)ethyl]trimethylammonium chloride,[2-methacrylamidoethyl]trimethylammonium chloride,[2-(acrylamido)ethyl]trimethylammonium chloride,N-methyl-2-vinylpyridinium chloride, N-methyl-1-vinylpyridiniumchloride, and mixtures thereof.
 5. The water-soluble or water-swellablecopolymer of claim 1, further comprising one or more comonomer B). 6.The water-soluble or water-swellable copolymer as claimed in claim 5,wherein the comonomer B) is selected from the group consisting ofunsaturated carboxylic acids, salts of unsaturated carboxylic acids,anhydrides of unsaturated carboxylic acids, esters of unsaturatedcarboxylic acids with aliphatic, olefinic, cycloaliphatic, arylaliphaticor aromatic alcohols having 1 to 22 carbon atoms, open-chain N-vinylamides, cyclic N-vinyl amides having a ring size of from 3 to 9, amidesof acrylic acid, amides of methacrylic acid, amides of substitutedacrylic acids, amides of substituted methacrylic acids, 2-vinylpyridine,4-vinylpyridine, vinyl acetate; styrene, acrylonitrile, vinyl chloride,vinylidene chloride, tetrafluoroethylene, vinylphosphonic acid or theesters or salts thereof, vinylsulfonic acid or the esters or saltsthereof, allylphosphonic acid or the esters or salts thereof,methallylsulfonic acid or the esters or salts thereof, and mixturesthereof.
 7. The water-soluble or water-swellable copolymer as claimed inclaim 1, wherein the polymeric additive E) is selected from the groupconsisting of polyalkylene glycol, alkylpolyglycol, and mixtures thereofor a homopolymer or copolymer of a compound selected from the groupconsisting of N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone,ethylene oxide, propylene oxide, acryloyldimethyltaurine,N-vinylcaprolactam, N-vinylmethylacetamide, acrylamide, acrylic acid,methacrylic acid, N-vinylmorpholide, hydroxymethyl methacrylate,diallyldimethylammonium chloride (DADMAC),[2-(methacryloyloxy)ethyl]trimethylammonium chloride (MAPTAC), andmixtures thereof.
 8. The water-soluble or water-swellable copolymer ofclaim 1, which is crosslinked.
 9. The water-soluble or water-swellablecopolymer of claim 1, wherein the copolymer is copolymerized byprecipitation polymerization in tert-butanol.
 10. The water-soluble orwater-swellable copolymer of claim 2, wherein R¹ is a radical selectedfrom the group consisting of vinyl, allyl, methallyl, methylvinyl,acryloyl, methacryloyl, crotonyl, senecionyl, itaconyl, maleyl, fumaryl,styryl, and mixtures thereof.
 11. The water-soluble or water-swellablecopolymer of claim 2, wherein the chemical bridge Y is selected from thegroup consisting of O—, —S—, —C(O)—, —C(O)—O—, —O—CH₂—CH(O—)—CH₂OH,—O—CH₂—CH(OH)—CH₂O—, —O—SO₂—O—, —O—SO₂—O—, —O—SO—O—, —PH—, —P(CH₃)—,—PO₃—, —NH—, —N(CH₃), and mixtures therefore.
 12. The water-soluble orwater-swellable copolymer of claim 2, wherein the repeating units A, B,C, and D originate from the group consisting of acrylamide,methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid,methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinylacetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide,diisopropylacrylamide, and mixtures thereof.
 13. The water-soluble orwater-swellable copolymer of claim 2, wherein the repeating units A, B,C, and D originate from ethylene oxide and/or propylene oxide.
 14. Thewater-soluble or water-swellable copolymer of claim 2, wherein v, w, x,and z independently of one another amount to from 1 to
 30. 15. Thewater-soluble or water-swellable copolymer of claim 3, wherein v and windependently of one another amount to from 1 to
 30. 16. A water-solubleor water-swellable copolymer obtained by free-radical copolymerizationof 50 to 99.5% by weight of acryloyldimethyltaurine and/oracryloyldimethyltaurate based on a total weight of said copolymer, saidacryloyldimethyltaurine and/or acryloyldimethyltaurate having a degreeof neutralization of more than 80%, with or in the presence of at leastone component selected from the group consisting of: a) one or morepolyolefinically unsaturated, macromonomer each having at least oneoxygen, nitrogen, sulfur or phosphorus atom and having a number-averagemolecular weight of greater than or equal to 200 g/mol, and b) one ormore olefinically unsaturated, cationic comonomer containing at leastone oxygen, nitrogen, sulfur or phosphorus atom and having a molecularweight of less than 500 g/mol, c) said copolymerization taking place inthe absence of at least one polymeric additive having number-averagemolecular weights of from 200 g/mol to 10⁹ g/mol.
 17. The water-solubleor water-swellable copolymer of claim 16, further comprising one or moreolefinically unsaturated, noncationic comonomer containing at least oneoxygen, nitrogen, sulfur or phosphorus atom and having a molecularweight of less than 500 g/mol.